Anti-static fuel composition

ABSTRACT

Anti-static fuel composition containing the reaction product of an organic hydroxy compound having the formula ROH in which R is a hydrocarbyl radical having from 2 to 30 carbon atoms and a fluorinated polymer from the group consisting of fluorinated polystyrene and fluorinated polypropylene.

United States Patent [1 1 Siegart et al.

[ Jan. 8, 1974 ANTI-STATIC FUEL COMPOSITION Inventors: William R.Siegart, Poughkecpsie,

N.Y.; William D. Blackley, Lake Elmo, Minn.; Harry Chafetz,Poughkeepsie, NY.

Assignee: Texaco Inc., New York, N.Y.

Filed: June 21, 1972 Appl. No.: 265,030

US. Cl 44/62, 44/79, 44/DlG. 2,

260/618 D, 260/633 Int. Cl Cl0l 1/16 Field of Search 44/62, 79, 66, DIG.2;

References Cited UNITED STATES PATENTS 5/1970 Wallet al. 260/618 D3,719,698 3/1973 'lcsoru ct ul 260K118 I) 3,677,725 7/1972 Andress, Jr.44/62 3,003,858 I0/l96l Andrcss, Jr. et a] 44/62 Primary Examiner-DanielE. Wyman Assistant Examiner-Y. Smith Attorney-Thomas H. Whaley et a].

10 Claims, No Drawings BACKGROUND OF THE INVENTION 1. Field of InventionDistillate hydrocarbon fractions, such as gasoline, kerosene, diesel oiland furnace oil, are highly inflammable materials and must be protectedfrom accidental ignition. Another property of these fuels is that theyare relatively non-conductive with respect to electricity.

Very large volumes of these liquid fuels are trans ferred daily throughpipelines, hoses and like equipment. Because the volumes are large, manytransfer operations are conducted using high velocity pumping means asin the loading of ships, storage tanks and aircraft. Because of thenon-conductive nature of these normally liquid hydrocarbons, staticelectricity builds up and accumulates in the fuel in the high speedpumping operations. This static electricity buildup is inherentlydangerous and is known to have caused disastrous fires and explosions inthe past.

The present invention is directed to novel reaction products whichprovide improved electrical conductivity characteristics to petroleumproducts. This invention also provides a novel method for preparinghydrocarbon soluble derivatives of insoluble fluorocarbons.

2. Description of the Prior Art Fluorinated hydrocarbons includingfluorinated polystyrene and fluorinated polyolefins are well known inthe art. Fluorinated polystyrene having the empirical formula (C l-l Fand a method for preparing these compounds is disclosed in U.S. Pat. No.3,380,983. According to this patent, a fluorinated polystyrene isprepared by contacting a polystyrene having a molecular weight betweenabout 10,000 and 500,000 with gaseous fluorine in the presence of analkali metal fluoride catalyst at a temperature between about 20 and 105C. The resulting products have the empirical formula (G l-I m where x is3 to 5 and having a melting point of 85 to 90 C.

A specific fluorinated styrene disclosed in this patent is representedby the empirical formula:

(clea s)...

SUMMARY OF THE INVENTION The anti-static fuel composition of theinvention comprises a mixture of hydrocarbons in the gasoline, kerosene,diesel oil and furnace oil boiling ranges containing a minor amount ofthe reaction product of an organic hydroxy compound with either afluorinated polystyrene or a fluorinated polypropylene. Morespecifically, the fuel composition, which will generally boil from about90 to about 750 F., contains an effective anti-static amount of thereaction product of an alcohol or phenol compound having the formulaROI-I in which R is a hydrocarbyl radical having from 2 to 30 carbonatoms and either a fiuorinated polystryrene represented by the empiricalformula:

( m a zOI in which x has a value from 3 to 5, or a fluorinatedpolypropylene represented by the empirical formula:

in which xhas a value from 20 to 40. The method for preparing thereaction product involves reacting the corresponding fluorinated polymerwith the prescribed organic hydroxy compound at a temperature in therange of 50 to 200 C. and in the presence of a catalyst from the groupconsisting of tertiary amines having the formula R N in which R is thesame or different aliphatic radicals having from 1 to 30 carbon atoms orthe alkali metal salt of the organic hydroxy compound having the formulaROM where M represents an alkali metal, such as sodium, potassium orlithium.

The preparation of the fluorinated polystyrene component of the reactionproduct of the invention having the empirical formula (C H F in which xis an average interger between 3 to 5 is fully described in U.S. Pat.No. 3,380,983 referred to above.

The fiuorinated polypropylene component of the reaction product of theinvention was prepared in essentially the same process used for thefluorinated polystyrene. In general, a solid polypropylene having aspecific gravity from about 0.880 to 0.908 is deposited on so diumfloride and dried and ground in a mill to pass through a l mm'screen.The treated polypropylene is charged to a reactor and the reactionmixture chilled. Fluorine diluted with nitrogen is added to the stirredreaction mixture until fluorine is detected coming from the reactor. Thereaction is then continued at room temperature until fluorine isdetected coming from the reactor at which time the reactor is heated toan elevated temperature about C. and the reaction continued untilfluorine issues from the reactor. The reactor is flushed with nitrogenand the fluorinated polypropylene recovered by solvent extraction asdisclosed in the abovenoted patent. The fiuorinated polypropyleneproduct has the empirical formula. (C HF L in which at has a value fromabout 20 to 40 preferably from 23 to 35. i

The fiuorinated polystyrene and fluorinated polypropylene noted aboveare reacted with the prescribed organic hydroxy compound to form thecorresponding alcohol or phenol reaction product which provides anti-static properties to liquid hydrocarbon fuels and fuel oilcompositions. In general, this method involves the reaction of afluorinated polymer. containing at least one unsubstituted hydrogen atomwith an organic hydroxy compound having the formula ROH in which R is ahydrocarbyl radical having from about 2 to 30 carbon atoms, the reactionbeing conducted in the presence of a tertiary amine or an alkali metalcatalyst. The preferred compounds are those in which R has a value from8 to 20 carbon atoms with the most preferred having from 12 to 18 carbonatoms. This reaction is generally conducted at a temperature in therange of 50 to 200 C. and preferably at a temperature from 80to C. t

The tertiary amine catalyst which can be employed in the reactionincludes trimethylamine, triethylamine, tripropylamine, tributylamine,triamylamine, trioctylaatoms. It is also understood that the Rs can becon 5 nected to form a cyclic tertiary amine compound.

The alkali metal catalyst which can be employed is the alkali metal saltof the organic hydroxy compound in the reaction. This catalyst isrepresented by the formula ROM where R is a hydrocarbyl radical havingfrom 2 to 30 carbon atoms and M represents an alkali metal, sodium,potassium or lithium.

The reaction is conducted using approximately one equivalent of theorganic hydroxy compound and two equivalent of the tertiary amine oralkali metal salt catalyst for each hydrogen atom in the fluorinatedpolymer.

The following examples illustrate the preparation of the organic hydroxycompound-fluorinated polymer reaction products of this invention.

EXAMPLE I PREPARATION OF THE ETHYL ALCOHOL DERIVATIVE OF CHLORINATEDPOLYSTYRENE 40 cc of absolute ethanol and 2.3 grams of freshly cutsodium were charged to a reaction vessel. After the sodium hadcompletely reacted, grams of fluorinated polystyrene having the formula(C, H F from US. Pat. No. 3,380,983 were charged to the reaction vessel,and the mixture refluxed for hours, cooled to room temperature, pouredinto 200 milliliters of water, filtered, and the solids washed anddried. A yield of 10.1 grams was obtained having a melting point of 170to 175 C. Analysis showed the presence of CH, olefin, CF and cyclohexaneabsorption. The product was soluble at room temperature and at reflux inacetone, tetrahydrofuran, ethyl acetate, acetic acid and diethyl ether.The product was not soluble at room temperature in dichloromethane,pentane, benzene, or water. Elemental analysis of the product showed:

% C 34.5 H 2.1 F 56.9

EXAMPLE II PREPARATION OF NONYLPHENOL FLUORINATED POLYSTYRENE REACTIONPRODUCT Sixth-six grams of nonylphonol, 200 ml. of 1,4- dioxane, and 7.0grams of sodium were refluxed until all the sodium was reacted.Fluorinated polystyrene (30 grams) was charged to the flask and themixture refluxed for 16 hours, diluted with an equal volume of pentaneand filtered. The solvent was removed from the filtrate under wateraspirator vacuum and the residue dissolved in pentane, filtered and thefiltrate extracted two times with alcoholic KOH (the alcoholic KOHsolution for each extraction was 100 ml. each of water and methanol and10 grams of KOH). The pentane was removed under water aspirator vacuumand the product dried. Yield 26 grams, color brown, melting point: 80-95C., infrared analysis confirmed the preparation of the desiredderivative. Elemental analysis: percent Carbon 45.8; percent Hydrogen4.6; percent Flourine 34.3; molecular wt. 3,930.

EXAMPLE III PREPARATION OF THE STEARYL ALCOHOL-FLUORINATED POLYSTYRENEREACTION PRODUCT 50 grams of fluorinated polystyrene similar to that inExample 1, 25 grams of triethylamine and cc of l,4-dioxane were refluxedtogether in a reactor, filtered, washed and dried.

59.4 grams of stearyl alcohol, 300 cc of 1,4-dioxane and 5.1 grams offreshly cut sodium were refluxed together in a separate vessel for 56hours, during which time all of the sodium had reacted. Theamine-treated fluorinated polystyrene was added to the stearylalcohol-sodium reaction mixture and the entire mixture refluxed for 16hours. The mixture was cooled to room temperature and filtered. Thesolvent was removed from the filtrate under water aspirator vacuum andthe residue extracted twice with 200 ml. portions of pentane. Thesolvent was then removed under the water aspirator vacuum and theresidue extracted with 100 ml 95 percent ethanol. The insoluble materialremaining (the desired product) was dried under reduced pressure. Yield19.2 g; melting point 48 C; infrared confirmed the product was analcohol derivative of fluorinated polystyrene, percent F 10.0, molecularwt. 439.

EXAMPLE IV PREPARATION OF LAURYL ALCOHOL DERIVATIVE OF FLUORINATEDPOLYSTYRENE 50 grams of fluorinated polystrene similar to Examle I 25grams triethylamine, and 200 cc of 1,4-dioxane were charged to a reactorand refluxed for 8 hours, filtered and the solvent removed under reducedpressure. The residue was combined with the solvent insoluble materialand then washed with water and dried.

41.0 grams of lauryl alcohol, 300 cc of 1,4-dioxane and 5.1 grams ofsodium were refluxed together in a second reactor for 34 hours duringwhich time the sodium completely reacted. The amine-treated fluorinatedpolystyrene from the first step was charged to the second reactor andthe mixture refluxed for 16 hours. The products were separated byfiltration. The insoluble material was dried and extracted with two 300cc portions of pentane and the pentane solution filtered. The insolublematerial was dried and extracted with two 400 cc portions'of water. Theinsoluble material (the desired product) was dried under reducedpressure. Yield 21.8 g; a brown solid melting point C. Infraredconfirmed the product was an alcohol derivative of flourinatedpolystyrene. The product was very slightly soluble both at roomtemperature and at reflux in tetrahydrofuran carbo tetrachloride, ethylacetate, acetone, benzene, 1,4-dioxane, isopropyl alcohol, ethylalcohol, methylene chloride, chloroform, methyl alcohol, diethylether,and Freon 1 13. It was insoluble both at room temperature and at refluxin pentane, FC-75 and water. Percent flourine 50.4.

30.0 of fluorinated polypropylene from Example I of U.S. Pat. No.3,652,238, 10.1 of triethylamine and 100 milliliters of 1,4-dioxane werecharged to a reactor, refluxed for 8 hours and filtered.

75 cc of lauryl alcohol and 2.9 grams of sodium were charged to a secondreactor and heated until the sodium had completely reacted. The aminetreated flourinated polypropylene and the sodium salt of lauryl alcoholwere combined and the stirred suspension heated at approximately 100 C.for 18 hours. The flask was cooled to room temperature and 200 cc of 95percent ethanol added. The suspension was filtered and the insolublematerial was dried under reduced pressure and extracted with two 250 ccportions of pentane. The pentane contained the desired product and wasseparated from the insoluble material by filtration. The pentane solventwas removed under water aspirator vacuum to yield a light viscous oil.Wt. 9.0 g; infrared analysis confirmed formation of the desired alcoholderivatives. Elemental analysis: percent Carbon 56.8; per cent Hydrogen8.7, mol. wt. 856.

The hydrocarbon base fuel for the fuel composition of the invention isany distillate hydrocarbon or-mixture of hydrocarbons in the gasoline,kerosene, diesel oil and/or furnace oil boiling ranges. In general,these normally liquid hydrocarbon fractions boil in the range from about90 to 750 F. The hydrocarbon mixture may consist of saturated andunsaturated aliphatic, cycloaliphatic and aromatic hydrocarbons withinthe noted boiling range. Specific fractions which can be employed forpreparing the fuel compositions of the invention include gasolineboiling from about 90 to 425 F., kerosene boiling from about 300 to 525F., gas oil and diesel oils boiling from about 390 to 750 F. and furnaceoils boiling from about 300 to 750 F. or higher.

The anti-static fuel composition of the invention is prepared byblending a minor anti-static effective amount of the prescribed additivein a base fuel. In general, the anti-static additive is employed at avery low concentration ranging from about 0.01 to 1,000 ppm. (weightparts per million parts of fuel). A preferred concentration range isfrom about 0.05 to 25 ppm, with the most preferred range being from 0.1to ppm.

The electrical conductivity or anti-static properties of the base fueland of the fuel compositions of the invention were determined in aResistivity Test according to ASTM Method D1 l69-64. In this test, theresistivity of fuel is tested by the electrical conductivity foundbetween two electrodes immersed in the fuel samples.

The base fuel employed in these tests was a typical turbine or jet fuelhaving the following inspection values:

API Grav., at 60F. 43.4

. ASTM Dist.,

IBP F. 334 10% 362 30 382 Net. Heat of Comb. BTU/1b 18,438

Luminometer No. 51.0

Freezing Point, F 64 Net Heat of Comb. BTU/gallon 124,200

The electrical conductivity of the fuel compositions expressed inResistance in ohm-cm is set forth in the following Table. The additiveconcentration employed was 1 ppm.

It is evident from the data that the anti-static fuel composition of theinvention is highly effective for improving the electrical conductivityof the hydrocarbon base fuel. These fuel compositions are considered tobe equal or superior in their anti-static properties to a fuelcomposition containing a commercial anti-static additive.

We claim:

1. A fuel composition comprising a mixture of hydrocarbons boiling fromabout to 750 F. containing a minor anti-static effective amount of areaction prod uct of an organic hydroxy compound having the for mula ROHin which R is hydrocarbyl radical having from ,2 to 30 carbon atoms anda fluorinated polymer selected from the group consisting of l) afluorinated polystyrene having the empirical formula:

(C H F where x has a value from 3 to 5, and 2) a fluorinatedpolypropylene having the formula:

(C HF where x has a value of 20 to 40.

2. A fuel composition according to claim 1 in which said fluorinatedpolystyrene has the formula:

3. A fuel composition according to claim 2 in which said organic hydroxycompound is ethyl alcohol.

4. A fuel composition according to claim 2 in which said organic hydroxycompound is nonylphenol.

5. A fuel composition according to claim 1 in which said fluorinatedpolypropylene has the empirical formula:

in which .x has a value from 23 to 35.

6. A fuel composition according; to claim 1 in which said organichydroxy compound is stearyl alcohol.

7. A fuel composition according, to claim 1 in which said organichydroxy compound is lauryl alcohol.

8. A fuel composition according to claim 1 in which the mixture ofhydrocarbons are in the gasoline and/or kerosene boiling ranges.

9. A fuel composition according to claim 1 in which the mixture ofhydrocarbons are in the furnace oil boiling range.

10. A fuel composition according to claim 1 containing from about 0.01to 1,000 weight parts per million parts of said reaction product of saidorganic hydroxy compound and said fluorinated polymer.

2. A fuel composition according to claim 1 in which said fluorinatedpolystyrene has the formula: (C16H3F25)3.87
 3. A fuel compositionaccording to claim 2 in which said organic hydroxy compound is ethylalcohol.
 4. A fuel composition according to claim 2 in which saidorganic hydroxy compound is nonylphenol.
 5. A fuel composition accordingto claim 1 in which said fluorinated polypropylene has the empiricalformula: (C3HF5)x in which x has a value from 23 to
 35. 6. A fuelcomposition according to claim 1 in which said organic hydroxy compoundis stearyl alcohol.
 7. A fuel composition according to claim 1 in whichsaid organic hydroxy compound is lauryl alcohol.
 8. A fuel compositionaccording to claim 1 in which the mixture of hydrocarbons are in thegasoline and/or kerosene boiling ranges.
 9. A fuel composition accordingto claim 1 in which the mixture of hydrocarbons are in the furnace oilboiling range.
 10. A fuel composition according to claim 1 containingfrom about 0.01 to 1,000 weight parts per million parts of said reactionproduct of said organic hydroxy compound and said fluorinated polymer.